Issue 2, 2002
From the journal:

Journal of the Chemical Society, Perkin Transactions 2

Torsional effects on reactivity in glycosyl transfer

Kathryn E. S. Dean,a   Anthony J. Kirby*a  and  Igor V. Komarov†a  

* Corresponding authors

a University Chemical Laboratory, Lensfield Road, Cambridge, UK

Abstract

The net effect of the four substituents on a hexapyranoside is to reduce reactivity at the anomeric centre by a factor of >107 compared with the parent tetrahydropyranyl acetal. The magnitude of the steric contribution to this factor is assessed by measuring the effect of four equatorial methyl groups on the rate of hydrolysis of 4-nitrophenyl tetrahydropyranyl acetal. Though the electronic effects of methyl substituents will be to increase the rate of hydrolysis, the net effect of the four equatorial methyl groups is a 4-fold decrease, evidence for an opposing steric effect estimated at two orders of magnitude. Torsional effects in a glycopyranoside thus contribute a factor of up to 50 towards the total of 107.

Graphical abstract: Torsional effects on reactivity in glycosyl transfer

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Article information

DOI
https://doi.org/10.1039/B106257N
Article type
Paper
Submitted
13 Jul 2001
Accepted
19 Nov 2001
First published
19 Dec 2001

J. Chem. Soc., Perkin Trans. 2, 2002, 337-341

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Torsional effects on reactivity in glycosyl transfer

K. E. S. Dean, A. J. Kirby and I. V. Komarov, J. Chem. Soc., Perkin Trans. 2, 2002, 337 DOI: 10.1039/B106257N

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